Draft for public hearing Swedish Society for Nature Conservation | Foundations concerning criteria for BRA MILJÖVAL Fragrances 2000 Draft for public hearing CONTENTS 1 INTRODUCTION 4 2 REPORT BASICS 4 2.1. Selection of chemicals 4 2.2. Collection of data 4 3 FRAGRANCES IN CLEANING AND CLEANSING PRODUCTS 5 3.1. Concentrations 11 3.2. Production and use volumes 12 3.3. Alternatives 15 3.4. Trends 16 3.5. Differences between countries. 18 4 RAW MATERIALS AND PRODUCTION 19 4.1. Introduction 19 4.2. Raw materials 19 4.3. Production 19 4.4. By-products and impurities 20 4.5. Waste disposal 21 4.6. Energy consumption 23 5 INHERENT PROPERTIES 23 5.1. Degradation 23 5.2. Ecotoxicity 26 5.3. Risk assessment 29 5.4. Human toxicity 31 5.4.1 Introduction 31 5.4.2 Acute toxicity 33 5.4.3 Chronic toxicity 33 5.5. Bioaccumulation 35 Foundations concerning criteria for BRA MILJÖVAL Perfumes 2000 2 Draft for public hearing 6 CHOICE OF ACTION/MEASURES 37 6.1. Regulations 38 7 RANKING 41 8 LACK OF DATA 43 9 REFERENCES 43 Foundations concerning criteria for BRA MILJÖVAL Perfumes 2000 3 Draft for public hearing 1 INTRODUCTION On behalf of The Swedish society for Nature Conservation, Norwegian Institute for Water Research (NIVA), has evaluated data for fragrance compounds in cleaning and cleansing products as a background document for criteria for Good Environmental Choice ("bra miljöval"). Cleaning and cleansing products include both household detergents like laun- dry, dishwashing and cleaning agents and "cosmetic products" like soaps, shampoos, conditioners, lotions, and so on. 2 REPORT BASICS 2.1. Selection of chemicals The selection of chemicals for this document should have been based on information from producers of cleaning and cleansing products, producers of fragrances and their professional and industrial bodies. The industry has not reported any chemical names or CAS-numbers of fragrance substances used in cleaning and cleansing products, due to complex formulations or confidentiality. Due to lack of data from the industry, chemical names or CAS-numbers are found from internet and other literature. For example are fragrance substances used for allergy testing and musk compounds discussed in this report. We expect that, at least, some of these substances are relevant for use in clea- ning and cleansing products. 2.2. Collection of data Data were collected from the producers of cleaning and cleansing products, producers of fragrances, their professional and industrial bodies (International Fragrance Association (IFRA)) and authorities. In addition handbooks, internet, databases and papers published in scientific journals were used.. A list of literature used for ecotoxicity data search is given in Appendix 1. Other references used are listed in the reference list. First we contacted producers of cleaning and cleansing products and their fragrance sup- pliers. None of the fragrance supplier wanted to answer us directly, but referred to their professional body IFRA. Even if our questions were specific, the information given by IFRA were general. No CAS numbers or ecotoxicity test data were given. The data we have found in literature must be used with caution. Safe conclusions and ranking is diffi- cult to make due to lack of data and unsafe data, but we have tried to summarise from the informations that are given in this report. Both test data and QSAR estimates are included if such data has been available. In most cases, the quality of the data could not be evaluated and in some cases only data of sup- posedly low quality were available. The last years, musk compounds have been much in focus as fragrance ingredients and more data have been available for musk compounds than for other fragrance substances. This fact may be conspicuous in this report, but some of the data relevant for musk com- pounds may also be relevant for other fragrance substances. Foundations concerning criteria for BRA MILJÖVAL Perfumes 2000 4 Draft for public hearing 3 FRAGRANCES IN CLEANING AND CLEANSING PRODUCTS Fragrance and extracts are used in many cleaning and cleansing products like soap, creams, lotions and oils, toiletries, bath preparations, detergents for dishwashing, laundry and washing machine and rinse aid. Fragrances are not used for their cleaning effect, but some fragrances and herb and spice extracts used as fragrances might have antimicrobial effect. In addition preserving agents added to the fragrance compounds might have antimicrobial effect. In detergents fragrances are added to give the product a pleasant odour during use and to impart a pleasing scent to clothes after they have been washed, dried and ironed. They camouflage unpleasant odour of other ingredients in the products and of dirt in the wash- ing water. They contribute nothing to the detergency of the formulation, but they do pro- vide aesthetic appeal. In fact, many consumers apparently associate the pleasant fra- grance with cleanliness and may even judge performance to some degree by this asso- ciation. Musks are important ingredients for the fragrance industry not only because of their typi- cal and unique smell, which determines the odour of a product to a great extent. In addi- tion, some of them have a positive effect on the quality of a fragrance. They make it more balanced and longer lasting because of their ability to bind fragrances to fabrics and to the skin. These substantive properties relate to their poor water solubility, the relatively low volatility and to their high solubility in organic solvents and tissues (OSPAR, 1999). A complete list of fragrance substances with CAS-numbers is not available because many of the fragrance substances are often unspecified compounds, which widely vary and often change. There have been much confidentiality regarding fragrances. Producers and fragrance organisations have used mysticism as a concept. Since the potential problems regarding these substances have been suggested, the authorities, consumers, and others have urged the industry to present more data for these substances. The producers of cleaning and cleansing products claim that the fragrance compositions are confidential and not accessible for them. The International Fragrance Association (IFRA) informs that the fragrances contain a large number of compounds. Which fra- grance mixes that are used in different fragrance variants is unknown for the producers of cleaning and cleansing products, but they suppose that the differences are small. As lit- erature regarding fragrance compounds they recommend Monografene, published in F. Cosmet. Toxicol. Vol 11, pp 95-115, pp 855-876, pp 1011-1081. This literature has not been available during this project. In a paper by Goronszy (1992) on treatment of wastewater from fragrance manufacturing further information on the composition of fragrances is presented. Fragrances contain 22 percent fragrance oils together with alcohol, dye solutions, water and propylene glycol with extenders, fixers and stabilizers. Various base fragrance oils are formulated to gen- erate specific olfactory effects in fragrance. Fragrances or perfumes consist of a combi- nation of numerous ingredients comprising single materials, complex reaction mixtures, basic odour components natural basically botanical or animal derived compounds. The actual formulae of fragrance compounds used by the industry are often patented. It is not uncommon to have some 250 identifiable compounds in a fragrance formulation. Many of these compounds are highly complex organics. Fragrances are extremely complex mixtures of chemicals and many include phenylpro- panals, cyclohexane derivates, tertiary alcohols, alkoxy-alkyl phenols, norborny deriva- tives, allylic alcohols, tricyclododecane derivatives, heterocyclic compounds, polycyclic Foundations concerning criteria for BRA MILJÖVAL Perfumes 2000 5 Draft for public hearing Diels – Alder adducts, α,β-dialkyl conjugated aliphatic nitriles, norsequiterpene deriva- tives, chain terpene alcohols, cycloalkylated aromatic nitriles, α-methylstyrene dimers or terpine dimers. Typical fragrance compounds include octadienes, hexyloxyacetonitriles, cyclopentane derivatives, α-oxo (oxo) sulfides, aliphatic dibasic acid diesters, 3-(10-undecenyloxy) propionitrile, tricyclodecane-methylol derivatives, 2-methyl-2-alkyl-alkanoic esters, tri- methylcyclonexylethyl ethers, cyanoethylidene-bicyclo-heptenes, crotonyl-trimethyl cy- clohexanes, nonanols, nonenols, α-oxo (oxo) mercaptanes, safranic acid esters and maltyl-2-methyl alkenoates (Goronszy 1992). Examples of some of these compounds, which are commonly used in the industry, are summarized in Table 1. Table 1. Examples of compounds and fragrances used in industry (from Goronszy 1992) Compound Fragrance 3-(4-tert-butyl-phenyl)-butanol-1 used for flower oil such as lavender, lily of the valley, linden, iris, lily, lilac, cycla- men 3-(4-hydroxy-4 methylcyclohexyl)-butanol mild floral odour of lilac or muguet 1-hydroxy-3 methoxyphenyl)-1-butene soft, flowery-sweet and hard mossy leather 2-cyclopropyl-4-isopropyl-2, 5,5-trimethyl- jasmine fragrance 1,3 dioxane 2-n-pentyl-3-(2-oxopropyl)-1- magnolia cyclopentanone methyl-1-ethynylcyclohexyl carbonate fruity, herbal complex odor distinctive of dill β-phellandrena (1-methylene-4-isopropyl-2- peppery, minty, refreshing, slightly citrusy cyclohexene odour 3-methylthio-2, 6 dimethyl-4-heptanone sweet, slightly floral and woody aroma with fruity and berry nuances A list of fragrance used in allergy testing may serve as a indication of types of fragrances